CN1104475C - Method and prepn. for mfg. molecular film - Google Patents
Method and prepn. for mfg. molecular film Download PDFInfo
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- CN1104475C CN1104475C CN97126413A CN97126413A CN1104475C CN 1104475 C CN1104475 C CN 1104475C CN 97126413 A CN97126413 A CN 97126413A CN 97126413 A CN97126413 A CN 97126413A CN 1104475 C CN1104475 C CN 1104475C
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/12—Applying particulate materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
- B05D1/283—Transferring monomolecular layers or solutions of molecules adapted for forming monomolecular layers from carrying elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
- B05D3/0486—Operating the coating or treatment in a controlled atmosphere
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention is to form a molecular film within the range from 1 nm to 0.1 mu m film thickness on a base material by using at least a silane-based compound and a solvent and causing elimination reaction between the base material and the silane-based compound and forming a siloxane bond. In the method for manufacturing a molecular film, a coating solution containing e.g. a chlorosilane-based compound is applied to the surface of a base material (2) having an active hydrogen on the surface and dehydrochlorination reaction is caused between active hydrogen on the surface of the base material and the chloro group of silane-based compound to covalently bond silane-based compound to the surface of the material. The material is sent into a chamber (11) held in a low steam concentration atmospheric state. A coating solution containing silane-based compound and a solvent is applied to the surface of the material by using transfer devices (6,7). Dehydrochlorination reaction is caused between the active hydrogen on the surface of the base material and the chloro group of silane-based compound. Thereafter, a nonreactive coating solution after the above-mentioned application is removed in the inside or the outside of the chamber.
Description
The present invention relates on substrate surface, form the preparation method and the preparation molecular film device of molecular film of the covalent linkage of silane based compound by siloxane bond.
What proposed is will have on the surface at the chlorosilane based compound that the molecular end that contains alkyl or fluoro-alkyl has a chloro silyl on the surface of glass etc. of active hydrogen to apply, and produces covalent linkage by the reaction that removes hydrogenchloride and forms molecular film.
Prior art be in the coating solution that contains the chlorosilane based compound dipping base material method (spy opens flat 1-70917 communique, EP0492545A).Other examples are to have proposed to make the chlorosilane based compound contact the method for reacting with substrate surface by gas.
But, though existing pickling process can be described as and forms thing at overlay film is on-plane surface, but under the situation of other shapes, can be on difform surface owing to carry out liquid reactions surfacewise the film forming excellent process of shape, but, it has to adopt a large amount of dipping solution, need pick and place the operation of base material, owing to complicated operation makes the operating time also very long, the result causes the problem of cost up, and, also there is short problem working lipe because chlorosilane based compound and moisture content react easily.And then because the chlorosilane based compound is all to carry out contact reacts on the base materials, under the situation that has the surface of not wishing to apply the chlorosilane based compound to exist, pickling process is unaccommodated.
And also there is the problem that is difficult to form even molecular film in the method that the chlorosilane based compound is reacted by gas contact substrate surface.
The object of the present invention is to provide a kind of above-mentioned existing problem that solves, reduce the solution amount that film forming needs, need not worry the working lipe of coating solution, the processing ease of base material carries out, and says the preparation method of the molecular film that cost is low and the preparation facilities of this film on the whole.
In order to achieve the above object, the preparation method of molecular film of the present invention has on the substrate surface of active hydrogen from the teeth outwards, apply to contain at least and have the chlorine of being selected from, the coating solution of the silane based compound of at least one reactive group in alkoxyl group and the isocyanato, remove reaction between the reactive group of the active hydrogen of substrate surface and above-mentioned silane based compound, the preparation method of the molecular film of covalent attachment silane based compound on substrate surface, it is characterized in that in the container that keeps low water vapor concentration atmosphere, putting into above-mentioned base material, use transfer device, on the surface of above-mentioned base material, apply the coating solution that contains silane based compound and solvent, make it between the reactive group of the active hydrogen of above-mentioned substrate surface and above-mentioned silane based compound, to remove reaction, afterwards within container or outside remove unreacted coating solution after the above-mentioned coating.
When in aforesaid method, using the chlorosilane based compound,, when using alkoxysilane compound containing trialkylsilyl group in molecular structure, take off ethanol synthesis as removing reaction as removing the reaction that reaction removes hydrogenchloride as the silane based compound.
Aforesaid method it is desirable to be provided with the inboard separation chamber around the part of coating solution at least that covers transfer device.Can and then prevent the hydrolysis reaction of the silane based compound in the coating solution thus.
And in aforesaid method, for the import of the above-mentioned base material of above-mentioned groove and outlet and ambient atmos are separated, it is ideal that air curtain is set.Can and then prevent the hydrolysis reaction of the silane based compound in the coating solution thus.
In aforesaid method, ideal be coated with impression method by with coating solution in unfolded technology on the support with will need to be coated with the technology of seal on the film forming base material of shape and form at unfolded solution on the above-mentioned support.Just reached the purpose that on base material, applies coating solution equably.
In aforesaid method, it is rolling method that ideal is coated with impression method.This is because this method can apply with very low cost, and can handle the base material width and be for example wide base material of 1-10 rice.
In aforesaid method, the silane based compound it is desirable to contain alkyl or fluoro-alkyl.If particularly contain fluoro-alkyl, can improve hydrophobicity, oleophobic property and didirtresistance.
In aforesaid method, it is ideal that solvent does not contain active hydrogen.If solvent contains active hydrogen, can react with silane compound.
In aforesaid method, it is ideal that the solvent that does not contain above-mentioned active hydrogen is selected from the wherein a kind of of hydrocarbon, siloxane-based compound and halohydrocarbon.
In aforesaid method, the ratio of mixture of silane based compound and solvent it is desirable to the content of silane based compound and is in the coating solution: 0.05-20 weight %, and also the dynamic viscosity of coating solution is 0.5-5000cst (at 25 ℃).Be suitable for rolling method.
Base material is a sheet glass in aforesaid method, and it is ideal that the one side relative with the coated side of coating solution forms overcover by resin film in advance.Though do not having under the situation of overcover, the non-coated side of coating also is unlikely to the degree that reacts with the silane based compound, has formed overcover and can protect non-coated side perfectly.
Secondly the preparation facilities of molecular film of the present invention be included in the separation chamber with base material from inlet move to the device of outlet, apply at above-mentioned substrate surface siliceous methane series compound and solvent coating solution transfer device and in said vesse, keep the device of low water vapor concentration atmosphere, it is characterized in that: within the above-mentioned separation chamber or outside equipped remove applying after the device of unreacted coating solution.
In the said apparatus preferably and then to be provided with what cover transfer device be inner side slot around the coating solution part at least.
The air curtain that the import of the above-mentioned base material of above-mentioned groove and outlet and outside air are separated preferably is set in the said apparatus.
Preferably keep the device of low water vapor concentration atmosphere preferably to feed in the said apparatus and contain water vapor concentration at 0kg/m
3-0.0076kg/m
3The device of the gas in the scope.
Transfer device is preferably by launching the device of coating solution on the support and will forming at the device that unfolded solution on the above-mentioned support is needing to be coated with seal on the film forming base material of shape in the said apparatus.
Transfer device it is desirable to roller coating device in the said apparatus.
Said apparatus further is provided with in inboard container the mode of low water vapor concentration gas is provided is ideal.
In the said apparatus, preferably the expansion that coating solution is carried out on above-mentioned support is by dripping to solution on the support, support is flooded in solution, the fog of solution, steam or solution is contacted with support and with solution attached on the support surface.
In said apparatus, above-mentioned roller coating device it is desirable at least by the coating control roller that is used to launch coating solution, is used for will applying on base material moltenly applying into the coating roll of uniform thickness and being used for from the back side of base material the backer roll that base material pushes out being constituted.
In said apparatus, the zone that above-mentioned roller ambient water vapor concentration is controlled in the above-mentioned numerical range comprises that the space of adhering to or be detained the part of above-mentioned solution at least on above-mentioned roller surface is an ideal.
In said apparatus, that the device of removing unreacted coating solution from above-mentioned substrate surface preferably is selected from is jet, heat that evaporation is removed, reduction vaporization is removed, dispel with gas and remove and clean with liquid at least one of removing etc. the device.
As mentioned above, the method according to this invention and device provide the required solution amount of minimizing film forming, need not pay close attention to the working lipe of coating solution, have carried out the preparation method who says the molecular film that cost is low on the whole of base material operation and the preparation facilities of film easily.
In the present invention, between base material and silane based compound, form siloxane bond, obtain on base material forming film thickness and be the molecular film of 0.1 nanometer-1 micron.
At this, above-mentioned silane based compound it is desirable to contain the compound of alkyl or fluoro-alkyl.What contain that the concrete example of compound of fluoro-alkyl can adopt is 17 fluoro 1,1, and general formulas such as 2,2 four decyl trichlorine siloxanes are C
nF
2n+1(CH
2)
2SiCl
3The fluoroalkyl silanes of (n is the positive integer of 1-30) expression.
And, the solvent that dissolves above-mentioned chlorosilane based compound can be do not contain can with the solvent of chlorosilane based compound reactive activity hydrogen.For example, above-mentioned fluoroalkylsiloxane compound is adducible is hydrocarbon system solvent, halohydrocarbon series solvent, alkylsiloxane series solvent, silicone oil solvent etc.If all kinds of SOLVENTS is represented with concrete example, be it is desirable to: the hydrocarbon system solvent is that turpentine wet goods general formula is C
nH
2n+2(n is a positive integer) or use C
nH
2nDeng the petroleum-type solvent of expression, the halohydrocarbon series solvent is that ten octafluoros are C for usefulness general formulas such as octanes
nH
2n-m+2X
mThe solvent of (n is that positive integer, m are that positive integer, X are halogens) expression.The alkylsiloxane series solvent is R such as hexamethyldisiloxane
1(R
2R
3SiO)
nR
4(n is positive integer, R
1, R
2, R
3, R
4Being alkyl) the straight chain shape silicone solvent or the prestox siloxanes etc. of expression be (R with general formula
1R
2SiO)
n(n is positive integer, R
1, R
2Be alkyl) cyclic solvent of expression, the perhaps any blended mixture of these solvents.
On substrate surface, be coated with the method for printing the solution that contains above-mentioned chlorosilane based compound and can enumerate rolling method and roll print process etc.For any method, on the roller, on the roll, the first-class regional water vapor concentration that has solution that becomes of substrate remains on 0kg/m
3-0.0076kg/m
3It in the scope ideal.
The chemosorbent of Shi Yonging can be enumerated following example in the present invention.
(1)CH
3(CH
2)
rSiX
pCl
3-p
(2)CH
3(CH
2)
sO(CH
2)
tSiX
pCl
3-p
(3)CH
3(CH
2)
u-Si(CH
3)
2(CH
2)
v-SiX
pCl
3-p
(4)CF
3COO(CH
2)
wSiX
pCl
3-p
But p represents the integer of 0-2, and r represents the integer of 1-25, and s represents the integer of 0-12, and t represents the integer of 1-20, and u represents the integer of 0-12, the integer that v represents 1-20, the integer that w represents 1-25.And X is hydrogen, alkyl, alkoxyl group, halogen-containing alkyl or halogen-containing alkoxyl group.
Enumerate (5)-(11) of the concrete adsorption compound of expression below.
(5)CH
3CH
2O(CH
2)
15SiCl
3
(6)CH
3(CH
2)
2Si(CH
3)
2(CH
2)
15SiCl
3
(7)CH
3(CH
2)
6Si(CH
3)
2(CH
2)
9SiCl
3
(8)CH
3COO(CH
2)
15SiCl
3
(9)CF
3(CF
2)
7-(CH
2)
2-SiCl
3
(10)CF
3(CF
2)
5-(CH
2)
2-SiCl
3
(11)CF
3(CF
2)
7-C
6H
4-SiCl
3
And it is chemosorbent that the chemosorbent of the isocyanate-based that whole chlorosilyl groups that for example can adopt (12)-(16) of expression are below replaced by isocyanato replaces above-mentioned chlorosilane.
(12)CH
3-(CH
2)
rSiX
p(NCO)
3-p
(13)CF
3-(CH
2)
rSiX
p(NCO)
3-p
(14)CH
3(CH
2)
sO(CH
2)
tSiX
p(NCO)
3-p
(15)CH
3(CH
2)
u-Si(CH
3)
2(CH
2)
v-SiX
p(NCO)
3-p
(16)CF
3COO(CH
2)
wSiX
p(NCO)
3-p
But p, r, s, t, u, v, w and X are identical with above-mentioned record.
Can adopt the concrete adsorption compound of following usefulness (17)-(23) expression to replace above-mentioned sorbent material.
(17)CH
3CH
2O(CH
2)
15Si(NCO)
3
(18)CH
3(CH
2)
2Si(CH
3)
2(CH
2)
15Si(NCO)
3
(19)CH
3(CH
2)
6Si(CH
3)
2(CH
2)
9Si(NCO)
3
(20)CH
3COO(CH
2)
15Si(NCO)
3
(21)CF
3(CF
2)
7-(CH
2)
2-Si(NCO)
3
(22)CF
3(CF
2)
5-(CH
2)
2-Si(NCO)
3
(23)CF
3(CF
2)
7-C
6H
4-Si(NCO)
3
And chemosorbent generally can adopt and use SiX
k(OA)
4-kThe material of (X is identical with above-mentioned record, and A is that alkyl, k are 0,1,2 or 3) expression.If wherein use CF
3-(CF
2)
n-(R)
q-SiX
p(OA)
3-p(n is the integer greater than 1, it is desirable to the integer of 1-22, R is alkyl, vinyl, ethynyl, allyl group, silicone base or the substituting group that contains Sauerstoffatom, q is 0 or 1, X, A are identical with above-mentioned record with p) expression material, have didirtresistance overlay film preferably though can form, also be not limited thereto, in addition, can also adopt CH
3-(CH
2)
r-SiX
p(OA)
3-pAnd CH
3-(CH
2)
s-O-(CH
2)
t-SiX
p(OA)
3-p, CH
3-(CH
2)
u-Si (CH
3)
2-(CH
2)
v-SiX
p(OA)
3-p, CF
3COO-(CH
2)
w-SiX
p(OA)
3-p(but p, r, s, t, u, v, w, X and A are identical with above-mentioned record).
And then adducible chemosorbent more specifically is shown in (24)-(47).
(24)CH
3CH
2O(CH
2)
15Si(OCH
3)
3
(25)CF
3CH
2O(CH
2)
15Si(OCH
3)
3
(26)CH
3(CH
2)
2Si(CH
3)
2(CH
2)
15Si(OCH
3)
3
(27)CH
3(CH
2)
6Si(CH
3)
2(CH
2)
9Si(OCH
3)
3
(28)CH
3COO(CH
2)
15Si(OCH
3)
3
(29)CF
3(CF
2)
5(CH
2)
2Si(OCH
3)
3
(30)CF
3(CF
2)
7-C
6H
4-Si(OCH
3)
3
(31)CH
3CH
2O(CH
2)
15Si(OC
2H
5)
3
(32)CH
3(CH
2)
2Si(CH
3)
2(CH
2)
15Si(OC
2H
5)
3
(33)CH
3(CH
2)
6Si(CH
3)
2(CH
2)
9Si(OC
2H
5)
3
(34)CF
3(CH
2)
6Si(CH
3)
2(CH
2)
9Si(OC
2H
5)
3
(35)CH
3COO(CH
2)
15Si(OC
2H
5)
3
(36)CF
3COO(CH
2)
15Si(OC
2H
5)
3
(37)CF
3COO(CH
2)
15Si(OCH
3)
3
(38)CF
3(CF
2)
9(CH
2)
2Si(OC
2H
5)
3
(39)CF
3(CF
2)
7(CH
2)
2Si(OC
2H
5)
3
(40)CF
3(CF
2)
5(CH
2)
2Si(OC
2H
5)
3
(41)CF
3(CF
2)
7C
6H
4Si(OC
2H
5)
3
(42)CF
3(CF
2)
9(CH
2)
2Si(OCH
3)
3
(43)CF
3(CF
2)
5(CH
2)
2Si(OCH
3)
3
(44)CF
3(CF
2)
7(CH
2)
2SiCH
3(OC
2H
5)
2
(45)CF
3(CF
2)
7(CH
2)
2SiCH
3(OCH
3)
2
(46)CF
3(CF
2)
7(CH
2)
2Si(CH
3)
2OC
2H
5
(47)CF
3(CF
2)
7(CH
2)
2Si(CH
3)
2OCH
3
The following describes the specific embodiment of the preparation facilities of the preparation method of film of the present invention and film.
" embodiment 1 "
Adopt conduct as example the preparation method of film and the preparation facilities of film to be described at this according to a kind of roller coat film deposition system in the preparation method's of the film of the present invention preparation facilities.And additive method outside this method is described simultaneously.
Fig. 1 is as the formation sketch according to the roller coat film deposition system of one of preparation facilities of the preparation method's of film of the present invention film.This roller coat film deposition system 1 is by base material 2 is put into separation chamber 11 from inserting mouthfuls 3, the film forming base material 5 of shape taken out and constitutes from exporting 4.Inside at device has by coating control roller 6, coating roll 7, transports roller 8, the nozzle 9 of the chlorosilane based compound that drips, provide the gas (exsiccant nitrogen) that contains the regulation water vapor concentration nozzle 10, be the container 11 of the water vapor concentration atmosphere that keeps regulation.
Though assembled for the nozzle 9 to the chlorosilane based compound solution that drips provide above-mentioned solution chlorosilane based compound solution storage tank, chlorosilane is provided is that the pump, waste liquid of solution reclaims utensil and recovery tube, because complicated and omit from figure.
Above-mentioned roller coat film deposition system constitutes by contacting or push with coating control roller 6 with coating roll 7, contact part to these two rollers provides the solution that contains chlorosilane based compound and solvent, by rotary coating roller 7, developing solution on the drum surface of coating roll 7.Be rotated owing to this coating roll 7 is contacted or pushes with the surface of base material 2, the solution on the cylindrical portions may surface of this coating roll is coated to substrate surface.Be coated with the base material that printed solution and be transported to the outlet 4 of roller coat film deposition system by transporting roller 8, the gas (drying nitrogen) that remains on the regulation water vapor concentration also to be provided during this period, can be removed by spontaneous evaporation forming useless solution or the solvent of film during this period.
The reaction that can carry out on base material has been described by aforesaid operations.The chlorosilane based compound can adopt 17 fluoro 1,1,2,2 four decyl trichlorine siloxanes, and solvent can adopt octamethylcyclotetrasiloxane.The concentration of chlorosilane based compound is 1 volume % solution.Junction at coating roll 7 and coating control roller 6 is provided with nozzle 9, and with the said nozzle above-mentioned solution that drips, the rotation by above-mentioned coating roll launches solution on the cylindrical portions may surface of above-mentioned coating roll equably.In the space that has above-mentioned solution, just the part at above-mentioned coating control roller and above-mentioned coating roll and said nozzle place forms lid, to its inner exsiccant nitrogen that feeds, confirms that above-mentioned spatial water vapor concentration is 0.0075kg/m
3Can suppress 17 fluoro 1 by the concentration that keeps this water vapour, 1,2, the silica-based hydrolysis of chloromethane of 2 four decyl trichlorine siloxanes, and can remove the moisture on above-mentioned coating roll, coating control roller surface or suppress it and adhere to, can also remove the excessive moisture of the substrate surface of sending into or suppress it and adhere to.Such formation, owing to contacting or extruding of base material of sending into and coating roll, unfolded solution can be coated to base material on the drum surface of coating roll.Fig. 2 represents to be in the mimic diagram of the substrate surface of this state.Have the group (being hydroxyl 22) of the active hydrogen that on base material 21 surfaces, exists and be coated with solute 17 fluoro 1 that print in the solution 23 in Fig. 2,1,2,2 four decyl trichlorine siloxanes (representing with ellipse briefly in Fig. 2) 24 form the film 25 with siloxane bond structure with the substrate surface that removes hcl reaction.Afterwards,, remove the solution that contains solute, when the solute total overall reaction, remove from substrate surface and to desolvate from substrate surface when on base material, existing when being not used in the solution of reaction.In addition, the state of film shown here is an example (explanatory view), has configuration certainly and is orientated different situations, also has the situation that forms than the thickness of this example.And much less can infer under Fig. 2 situation and can not react from a side, carry out the film forming reaction of shape everywhere simultaneously at substrate.
This be illustrated in the difform base material of present embodiment on be coated with the seal solution example.The example that Fig. 3 comes to this.In Fig. 1, will contain under the drips of solution of chlorosilane based compound and solvent, but dip roll 31 will be set in this example, at groove (バ from nozzle 9
StarDe) etc. in the container above-mentioned dip roll is flooded in above-mentioned solution 32.Operate cylindrical portions may surface and the inner all dipping of above-mentioned solution by this with dip roll.Above-mentioned dip roll is contacted with coating roll 33, above-mentioned solution is coated with on the cylindrical portions may surface that is imprinted on above-mentioned coating roll, and then can be by being coated with the impression film forming on base material 34 surfaces identical with the embodiment of Fig. 1.
Fig. 4 does not use Fig. 1 and roller shown in Figure 3 to carry out that solution is coated with the form of seal and the situation of using cloth to carry out.Use continuously liner to be provided with as shown in Figure 4 with 41.This band be suitable for be rubber or perviousness weaving shape band etc.The part of band is by in the cloud case 42 that is formed by above-mentioned solution, and the above-mentioned band that passes through contacts with base material 43 surfaces with roller 44, and unfolded solution is coated on substrate surface on tape.The processing of carrying out afterwards is the same with the explanation of using at Fig. 1.
The solution that is coated with seal on substrate surface forms film by reaction as shown in Figure 2, for forming useless solution of film or solvent according to transporting spontaneous evaporation on the roller in the used explanation of Fig. 1.At this water vapor concentration that transports roller segment during greater than prescribed value, the chlorosilane based compound that is coated with seal on substrate surface not only forms film with the hydroxyl reaction of substrate surface, and react simultaneously between the above-mentioned chlorosilane based compound, this reaction forms the chain lock shape and polymerization takes place.Take place for fear of this situation, water vapor concentration must be remained in the numerical value of regulation.Under the state in water vapor concentration remains on the regulation numerical range, can list the additive method outside the spontaneous evaporation.Under the state in water vapor concentration remains on the regulation numerical range, can adopt the method that is blown into high temperature drying nitrogen, will be dissolved in the coating solution easily and exsiccant solution easily, be method that spurting is blown into, transporting the drying means (air knife) that the part in the way reduces pressure and accelerates the exsiccant method or be blown into the high pressure draft of dry gas in outlet base material to outlet with transporting roller.At this, be blown into the method (air knife) of the high pressure draft of dry gas in outlet, except to substrate surface dry useful, also keep the water vapor concentration atmosphere aspect of regulation also effective, in order to reach this purpose, it not only is arranged on the outlet of device, and it also all is suitable also can being arranged on inlet.
" Comparative Examples 1 "
In order to determine preparation method's of the present invention effect, prepare film with prior preparation method with chlorosilane key.Keep the record among water vapor concentration role such as the embodiment, simultaneously also example do not keep the situation of water vapor concentration.Carry out comparison aspect the expense in the pickling process of this and existing method.
Use 17 fluoro 1,1 in the same manner as chlorosilane based compound and present embodiment, 2,2 four decyl trichlorine siloxanes, solvent uses octamethylcyclotetrasiloxane, it is mixed with the solution of 1 volume % in groove.The groove atmosphere of having put into above-mentioned solution is remained on the water vapor concentration shown in the front, flood the sheet glass suitable with A4 paper.Dipping time is 15 minutes, afterwards solvent is carried out 15 minutes seasoning.
Film is formed the condition of surface of finishing sheet glass afterwards, measure with the water droplet and the formed angle of sheet glass (contact angle) of dripping.
Table 1
Preparation method's prior preparation method of contrast project embodiment 1 (Comparative Examples 1)
(rolling method) (pickling process)
Contact angle 112 degree 112 degree
The outward appearance visual inspection does not have dirt settling to adhere to the gonorrhoea thing
Preparation liquid measure 0.4g 200g
Film formation time 15 seconds 1800 seconds
Table 1 is to adopt the method shown in the embodiment forming under the film situation on the A4 sheet glass and adopting the method shown in the Comparative Examples equally at the comparison sheet that forms contact angle, outward appearance visual inspection, preparation liquid measure and film formation time under the film situation on the A4 sheet glass.We can say that the contact angle of measuring the film that comes all is 112 degree, condition of surface is all identical.In existing method, water vapor concentration has produced the gonorrhoea dirt settling, and in method shown in the present, can not determine such dirt settling not within the limits prescribed on sheet glass owing to flood afterwards during by the outward appearance visual inspection on the one hand.
And the method according to this invention, the solution amount of the chlorosilane cpd that uses on sheet glass is 0.4 gram, in the conventional method in order to prepare that required solution needs 200 of dipping A4 sheet glass restrain or 500 times solution amount.But, in the conventional method, even two substrates of dipping in the solution that is a plate preparation, owing to contain the required chlorosilane based compound of enough formation films, certainly also can film forming, in order on the polylith base material, to form film, not talkative all will be with 500 times solution, but in preparation method of the present invention, adopt and whenever carry out one-pass film-forming and just can finish film forming with the solution of appropriate amount, on the one hand, even since in existing pickling process a substrate film forming, also need to prepare the solution of 200 grams in this example, be the more superior of preparation method of the present invention when at this moment requiring to carry out film forming according to preparation.Just only because this reason can be cut down the required expense of film forming.Even the keeping quality of comparison solution, it is better also to can be described as the inventive method.
Secondly, on film formation time, there is evident difference.Just can make a sheet glass film forming in 15 seconds in an embodiment of the present invention, and can determine it is by the no problem film of outward appearance visual inspection.But in existing preparation method's dipping method, need 1800 seconds, or 120 times of film formation time of the present invention, the Products Quality that makes is also good inadequately.Film forming quantity is also different greatly in unit time in this respect, can know that in preparation method of the present invention aspect the reduction film forming expense be good.
If the difference of expression the present invention and existing dipping method others, the formation face of film is to form at face in the present invention, in contrast, is forming the film two sides in the conventional method.Only needing to form under the situation of a facial mask, when adopting the method for having now, need cover in advance by some means does not need film forming, makes the film forming reaction of shape does not take place.And, to form the situation of a facial mask for the result, existing method is not needing to have formed unnecessary film on film forming owing to be to form film on two faces, and has the shortcoming that makes the film forming cost increase twice.
" embodiment 2 "
The embodiment of printing process is padded in expression below.Fig. 5 is the mimic diagram that pads printing process.The chlorosilane based compound uses positive decyltrichlorosilane and 17 fluoro 1,1, two kinds of 2,2 four decyl trichlorine siloxanes.Solvent uses the perfluoro octane.The strength of solution of chlorosilane based compound separately is 0.1 volume %.The Glass Containers 51 of putting into this solution is arranged on water vapor concentration remains on 0.007kg/m
3Separation chamber in.In padding printing, use the seal shape to pad equipment 52, pad at this and pasting rubber 53 on printing surface.Rubber be shaped as 30 millimeters * 50 millimeters.This rubber face of dipping in the solution of making by above-mentioned positive decyltrichlorosilane.This rubber is as the support that solution is transferred on the substrate.Then on A4 sheet glass 54, push rubber face (shown in arrow among the figure), solution is coated with seal on the face of sheet glass.Until solvent on the glass surface till the seasoning.Then adopt other to pad equipment equally with 17 fluoro 1,1,2,2 four decyl trichlorine siloxane solutions are coated with and print on the sheet glass, wait for until seasoning.Above-mentioned technology is by dry air water vapor concentration to be remained on 0.0071kg/m
3The space carry out.The sheet glass of having finished aforesaid operations is taken out from the space of control water vapor concentration, measure contact angle by aforesaid same water droplet.
The contact angle of film at the place of formation that is formed by positive decyltrichlorosilane is 100 degree, and be corresponding to therewith 17 fluoro 1,1, and the film that 2,2 four decyl trichlorine siloxanes form is 111 degree at the contact angle of formation place.The difference of the contact angle that Here it is is caused by various materials.On the one hand, there is not the contact angle in the film forming place of shape less than 30 degree.And, to in water, flood by padding the above-mentioned sheet glass that print process formed film, if only demonstrate when from water, taking out in the film forming place of shape, be that 30 millimeters * 50 millimeters shape does not get wet significantly, there is not the film forming part of shape by water-moistened phenomenon.Can provide and the difform glass substrate of rolling method shown in the embodiment 1 only at the film forming part formation of needs shape film if print process is padded in use thus.
" embodiment 3 "
The foregoing description all is that support is the solid example, and expression is the example of liquid below.
Fig. 6 adopts the mimic diagram of liquid as the technology of support.The chlorosilane based compound adopts 17 fluoro 1,1, and 2,2 four decyl trichlorine siloxanes, solvent adopt chain silicon oil mixture (the straight chain dimethyl silicone oil of eastern レ ダ ウ conning silicone Co., Ltd. preparation), and compound concentration is the solution 61 of 0.1 volume %.Support need be and above-mentioned chain silicon oil mixture and the immiscible liquid of above-mentioned positive decyltrichlorosilane that adopting fluorine at this is liquid 62 (preparation of Off ロ リ Na-ト (trade mark) Sumitomo 3M Co., Ltd.).Remain on 0.0063kg/m at water vapor concentration
3Enclosed space in place 15 centimetres of leg-of-mutton containers 63, be each corner that liquid fully expands to container with above-mentioned fluorine therein, the solution made by the mixture of positive decyltrichlorosilane and chain silicone oil about 10 milliliters thereon reposefully drips.
Is to launch equably on the solution above-mentioned solution at fluorine.The dipping diameter is 3 inches a silicon substrate in this container, upwards takes out (shown in arrow among the figure) at once, and evaporating solvent is until drying like this.On silicon substrate, form the film that forms by positive decyltrichlorosilane according to aforesaid operations.
Though used glass baseplate and silicon substrate in the above-described embodiments,, do not had the material problem with other base materials that has active hydrogen to come out from the teeth outwards.Various metals, metal oxide, pottery, plastics that satisfy above-mentioned condition etc. also are effective.
And, though be presented as in the present embodiment the water vapor concentration regulation is remained on 0kg/m
3-0.0076kg/m
3The nozzle that gas is provided in the scope, if but do not resemble and provide gas the present embodiment, and when moisture absorption apparatus etc. being set also can being controlled at water vapor concentration in the specialized range, also be feasible not according to the method for present embodiment.In addition for needing to be provided with gas barrier under the situations such as method that gas is provided.These equipment have been omitted in the present embodiment.
" embodiment 4 "
Fig. 7 represents to be coated with as employing the formation sketch of a kind of roller coat in the preparation facilities of film of seal method.In the separation chamber 71 of this roller coat 70, be provided with the import 72 and the outlet 73 of base material 81, be provided with elements such as coating control roller 74, coating roll 75, rear roller 87 in inside.By the transporter of the base material represented with roller 76 grades, will be by the inlet 72 the substrate passed coating rolls 75 that enter from exporting outside 73 carrying devices.Coating is put into the solution that contains the silane based compound 78 of the base material of container 77, extracts out with the pipeline 80a that has equipped pump 79, supply to periphery between coating control roller 74 and the coating roll 75 from pipeline 80b on.The air knife 84 and 85 provide respectively with the gas (suitable is drying nitrogen or dry air) of the 82 and 83 low water vapor concentrations of representing is provided in inlet 72 and outlet 73.And the lid 86 (inside groove) that covers coating control roller 74 and coating roll 75 tops is set, by the gas (suitable is drying nitrogen or dry air) 89 of low water vapor concentration is provided in this lid from pipeline 88, can make its water vapor concentration on every side remain on the desirable 0.0076kg/m of being lower than
3(being equivalent to 25 ℃ of relative humidity) less than 35%.In addition, though the part that Fig. 7 is expressed as except that import and outlet is sealed, but still can be set to suitably discharge the ventilation escape route of other materials outside desolventizing.
In above-mentioned rolling method, by coating roll 75 is contacted or pushes with coating control roller 74, provide the solution that contains the silane based compound in this section, a rotary coating roller 75, this solution are equably on the cylinder outer surface attached to coating roll 75.And then by this coating roll 75 is contacted or push rotation with base material 81 surfaces, this solution can be coated on the substrate surface equably.And because the low water vapor concentration of the inner maintenance of device can prevent that before removing hydrogenchloride silane based compound that applies and the moisture in the cloud and mist atmosphere react on base material.
These embodiment are owing to providing the solution that contains the silane based compound at least on the cylinder outer surface at the coating roll of roller coat under the low water vapor concentration atmosphere, be rotated by this coating roll is contacted or pushes with substrate surface simultaneously, above-mentioned solution is coated in (A of Fig. 7) on the substrate surface.At this moment, the silane based compound forms as shown in the formula the covalent linkage shown in 1 with surperficial hydroxyl generation condensation reaction, silane based compound and substrate surface.
(formula 1)
Afterwards, this base material is dry under the low water vapor concentration atmosphere of roller coat inside, and solvent and the base material bonded silane based compound (B of Fig. 7) that does not have with coating solution removed in evaporation.Residual on base material like this have a silane based compound that forms covalent linkage with substrate surface.And then this base material contacted with the air that contains moisture of roller coat outside, take place as shown in the formula the hydrolysis reaction shown in 2.
(formula 2)
If then under dry atmosphere, carry out drying (C of Fig. 7), take place as shown in the formula the condensation reaction between 3 the silane based compound, form the film that produces covalent linkage by siloxane bond and substrate surface.
(formula 3)
In addition, can carry out in the outside of separation chamber 71 in the technology shown in the B of Fig. 7.
Adopt above-mentioned preparation facilities, can prepare film with siloxane bond.That is to say that the material of coating roll 75 and coating control roller 74 can adopt isobutylene-isoprene copolymer.Silane based compound chemical formula C
8F
17(CH
2)
2SiCl
3The fluoro-alkyl trichlorosilane of expression, solvent adopt the solution by the 1 volume % for preparing as the octamethylcyclotetrasiloxane of non-water solvent.For coating roll 75, coating control roller 74 and roller coat 70 inside are under the low water vapor concentration atmosphere, provide water vapor concentration to be lower than 0.03kg/m
3Nitrogen.
Will be up as the end face of the float glass of base material 81, make it to go up and form the overlay film that constitutes by the silane based compound and be transported in the roller coat for superincumbent.For the face below the above-mentioned float glass is not contacted with the silane based compound, use the coating film covering formation overcover that forms by poly-terephthalic acid ethyl ester.The glass baseplate that in separation chamber, provides by adjusting coating roll 75 coating control roller 74 and to the amount of base material 81 extruding, at room temperature with above-mentioned solution on the surface of float glass equably coating thickness be the film of 0.5-1 micron.To the position of this float glass at Fig. 7 B, employing contains water vapor concentration and is lower than 0.03kg/m afterwards
3Drying nitrogen carry out drying.And then, float glass is taken out to the outside from separation chamber, and under the atmosphere of the air that contains moisture content, carry out drying.Under this situation that has moisture content, condensation reaction takes place between the silane based compound that applies on the float glass, form by the film of siloxane bond with substrate surface generation covalent linkage.Afterwards, remove above-mentioned coating film.This float glass can form the hydrophobic surface and the oleophobic face of covalent linkage effectively as the residue composition that has the silane based compound in the outside, have the glass that is formed overcover by coating film in the inboard.
Film according to the invention described above can form film on the tabular base material, with existing dipping method mutually specific production rate be greatly improved, preparation cost reduces significantly.Therefore it has very big industrial value.
The simple declaration of accompanying drawing:
The sketch of the roller coat film deposition system of the preparation facilities of the molecular film of Fig. 1-one embodiment of the invention.The mimic diagram of substrate surface when Fig. 2-solution is coated with seal on substrate surface.Fig. 3-have with the difform base material of Fig. 1 on be coated with the example of seal.Fig. 4-on base material, carry out the example that solution is coated with seal with cloth.Fig. 5-pad mimic diagram of printing process.Fig. 6-employing liquid is as the mimic diagram of the technology of support.The sketch of the roller coat film deposition system of the preparation facilities of the molecular film of Fig. 7-other embodiments of the invention.The base material 3-that the explanation 1-roller coat film deposition system 2-of symbol forms overlay film inserts mouthful film forming base material 6-of 4-outlet 5-shape coating control roller 7-coating roll 8-, and to transport the roller 9-chlorosilane that drips be the nozzle that the nozzle 10-of solution provides the gas (drying nitrogen) with regulation water vapor concentration.11-keeps the container of water vapor concentration in specialized range.21-base material 22-exists group (being hydroxyl among the figure) 23-of active hydrogen to be coated with seal solution 24-17 fluoro 1 from the teeth outwards, 1,2,2 four decyl trichlorine siloxanes (representing with ellipse among the figure) 25-have the film 31-dip roll 32-that forms the siloxane bond structure with substrate surface and put into Glass Containers 52-that cloud case 43-base material 44-roller 51-that the solution 33-coating roll 34-base material 41-of container such as groove forms with 42-solution continuously puts into solution to pad equipment 53-rubber 54-sheet glass 61-solution 62-fluorine be liquid 63-groove 64-silicon material
Claims (21)
1. the preparation method of a molecular film, it is that the coating solution that applies the silane based compound that contains at least a reactive group that is selected from chloro, alkoxyl group and isocyanato on the substrate surface of active hydrogen is arranged from the teeth outwards, make between the reactive group of the active hydrogen of substrate surface and above-mentioned silane based compound and remove reaction, make the silane based compound form the method that covalent linkage prepares molecular film at substrate surface, it is characterized in that
In the separation chamber under the atmosphere state that keeps low water vapor concentration, send into above-mentioned base material, use transfer device, on above-mentioned substrate surface, apply the coating solution that contains silane based compound and solvent, make between the reactive group of the active hydrogen of above-mentioned substrate surface and silane based compound and remove reaction, unreacted coating solution is removed after will applying in container or outside the container afterwards.
2. according to the preparation method of the molecular film of claim 1 record, wherein, also be provided with being the inner side slot that covers around the coating solution part at least in the transfer device.
3. according to the preparation method of the molecular film of claim 1 record, wherein, be provided with air curtain for base material entrance and exit in the above-mentioned separation chamber and outside air are separated.
4. according to the preparation method of the molecular film of claim 1 record, wherein, described transfer device by launch the technology of coating solution on the support and with above-mentioned support on the unfolded solution technology that needing to be coated with seal on the film forming base material of shape form.
5. according to the preparation method of the molecular film of claim 1 record, wherein, described transfer device is a roller coating device.
6. according to the preparation method of the molecular film of claim 1 record, wherein, described silane based compound contains alkyl or fluoro-alkyl.
7. according to the preparation method of the molecular film of claim 1 record, wherein, described solvent is the solvent that does not contain active hydrogen.
8. according to the preparation method of the molecular film of claim 7 record, wherein, the described solvent that does not contain active hydrogen is selected from least a in hydrocarbon, siloxane-based compound and the halohydrocarbon based compound.
9. according to the preparation method of the molecular film of claim 1 record, wherein, the ratio of mixture of silane based compound and solvent in the described coating solution is expressed as with the content of silane based compound: the scope of 0.05-20 weight %, and this coating solution is 0.5-5000cst 25 ℃ dynamic viscosity.
10. according to the preparation method of the molecular film of claim 1 record, wherein, described base material is a sheet glass, forms overcover with resin film in advance in the one side opposite with the coated side of coating solution.
11. the preparation facilities of a molecular film, it comprises:
In separation chamber, the base material that has active hydrogen on the surface is moved to the device of outlet from inlet;
For transfer device, the described silane based compound that applies the coating solution that contains silane based compound and solvent on above-mentioned substrate surface contains at least a reactive group that is selected from chloro, alkoxyl group and the isocyanato;
Make the device that remains in low water vapor concentration atmosphere state in the above-mentioned separation chamber;
In addition, among said vesse or outside also have the device that unreacted coating solution after applying is removed.
12. according to the preparation facilities of the molecular film of claim 11 record, wherein, it also is provided with a kind of is the inner side slot that covers around the coating solution part to transfer device at least.
13., wherein, be provided with the entrance and exit of the above-mentioned base material of above-mentioned separation chamber and the air curtain that outside air separates according to the preparation facilities of the molecular film of claim 11 record.
14. according to the preparation facilities of the molecular film of claim 11 record, wherein, the described device that low water vapor concentration atmosphere is kept is at 0kg/m with water vapor concentration
3-0.0076kg/m
3The device that gas in the scope feeds.
15. according to the preparation facilities of the molecular film of claim 11 record, wherein, described transfer device is by the device that launches coating solution on support, and will the above-mentioned device formation that is needing to be coated with on the film forming base material of shape seal at unfolded solution on the support.
16. according to the preparation facilities of the molecular film of claim 11 record, wherein, described transfer device is a roller coating device.
17. the preparation facilities according to the molecular film of claim 12 record wherein, also is provided with the device of the gas that low water vapor concentration is provided in inner side slot.
18. preparation facilities according to the molecular film of claim 15 record, wherein, described is by solution is dripped on the support at the device that launches coating solution on the support, support is flooded in solution, the mist of solution, steam or solution is contacted with support and with solution attached to the lip-deep device of support.
19. preparation facilities according to the molecular film of claim 16 record, wherein, described roller coating device be at least by the coating control roller that is used to launch coating solution, be used on base material coating solution applied into the coating roll of uniform thickness and be used for constituting from the backer roll of substrate backside extruding base material.
20. according to the preparation facilities of the molecular film of claim 14 record, wherein, it is to be included in the space of adhering to or be detained the part of above-mentioned solution on the surface of above-mentioned at least roller that the water vapor concentration around the above-mentioned roller is controlled at zone in the above-mentioned numerical range.
21. preparation facilities according to the molecular film of claim 11 record, wherein, the described device of removing unreacted coating solution from substrate surface is to be selected from jet flow stream, to heat up that evaporation is removed, reduction vaporization is removed, to dispel with gas and remove and wash by liquid at least a device of removing the device.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP296649/1996 | 1996-11-08 | ||
| JP296649/96 | 1996-11-08 | ||
| JP29664996 | 1996-11-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1192458A CN1192458A (en) | 1998-09-09 |
| CN1104475C true CN1104475C (en) | 2003-04-02 |
Family
ID=17836281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97126413A Expired - Lifetime CN1104475C (en) | 1996-11-08 | 1997-11-08 | Method and prepn. for mfg. molecular film |
Country Status (4)
| Country | Link |
|---|---|
| US (2) | US5948476A (en) |
| EP (1) | EP0841099A1 (en) |
| KR (1) | KR100239159B1 (en) |
| CN (1) | CN1104475C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100445432C (en) * | 2003-12-24 | 2008-12-24 | 松下电器产业株式会社 | Substrate for use in crystallization and method for producing the same |
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| TW422822B (en) * | 1996-04-04 | 2001-02-21 | Matsushita Electric Ind Co Ltd | Contamination-resistant float glass and process for producing the same as well as cooking device using said contamination-resistant float glass |
| IT1291710B1 (en) * | 1997-05-30 | 1999-01-21 | Gilles Picard | METHOD AND EQUIPMENT FOR THE PREPARATION OF MONOLAYER FILM OF PARTICLES OR MOLECULES. |
| US6281921B1 (en) * | 1999-02-15 | 2001-08-28 | Riso Kagaku Corporation | Method for treating the surface of thermal printing heads |
| US6485785B1 (en) * | 1999-08-31 | 2002-11-26 | Matsushita Electric Industrial Co., Ltd. | Coating film, and method and apparatus for producing the same |
| KR100368203B1 (en) * | 2000-07-11 | 2003-01-24 | (주)거명 | A producing method of toner binder resin composition |
| DE10101369A1 (en) * | 2001-01-13 | 2002-07-18 | Itw Oberflaechentechnik Gmbh | Spraying method and spraying device for coating liquid |
| DE10101372A1 (en) * | 2001-01-13 | 2002-08-01 | Itw Oberflaechentechnik Gmbh | Spraying method and spraying device for coating liquid |
| CN1283372C (en) | 2001-04-02 | 2006-11-08 | 松下电器产业株式会社 | Water-repellent film and method for preparing the same, and ink-jet head and ink-jet type recording device using the same |
| US6846454B2 (en) * | 2001-12-24 | 2005-01-25 | Agilent Technologies, Inc. | Fluid exit in reaction chambers |
| US6666936B1 (en) | 2002-02-28 | 2003-12-23 | The Regents Of The University Of California | Energetic powder |
| US6855375B2 (en) * | 2002-03-28 | 2005-02-15 | Matsushita Electric Industrial Co., Ltd. | Method for producing water-repellent film |
| CN100514065C (en) * | 2003-08-27 | 2009-07-15 | 松下电器产业株式会社 | Microchip, process of manufacturing the same, and analytical method using the same |
| US7654010B2 (en) * | 2006-02-23 | 2010-02-02 | Tokyo Electron Limited | Substrate processing system, substrate processing method, and storage medium |
| TWI402235B (en) | 2010-07-30 | 2013-07-21 | Univ Nat Formosa | Mixed self - assembled molecular structure with antibacterial properties and its preparation method |
| US8973401B2 (en) | 2010-08-06 | 2015-03-10 | Corning Incorporated | Coated, antimicrobial, chemically strengthened glass and method of making |
| SG192011A1 (en) | 2011-01-17 | 2013-08-30 | Orthodyne Electronics Corp | Systems and methods for processing ribbon and wire in ultrasonic bonding systems |
| TWI524948B (en) * | 2012-01-17 | 2016-03-11 | Kabushikikaisha Miyako Roller Kogyo | A coating method for a functional coating agent for a substrate, and a coating device for a functional coating agent |
| JPWO2014077371A1 (en) * | 2012-11-16 | 2017-01-05 | 旭硝子株式会社 | Glass manufacturing method and glass manufacturing apparatus |
| CN104513950B (en) * | 2014-10-29 | 2019-10-01 | 苏州东杏表面技术有限公司 | A method of quickly preparing wear-resisting anti-soil film |
| US11117073B2 (en) * | 2016-07-11 | 2021-09-14 | Hewlett-Packard Development Company, L.P. | Froth coalescing vent |
| CN114405293B (en) * | 2021-08-06 | 2023-07-14 | 江苏九天高科技股份有限公司 | Preparation method and device of flat molecular sieve membrane |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR19980042237A (en) | 1998-08-17 |
| US5948476A (en) | 1999-09-07 |
| EP0841099A1 (en) | 1998-05-13 |
| CN1192458A (en) | 1998-09-09 |
| US6183558B1 (en) | 2001-02-06 |
| KR100239159B1 (en) | 2000-01-15 |
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